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It is shown here that random chain scission is a very minor reaction from the chemical point of view, but has a profound effect on the rheological properties of polymers by virtue of their long-chain nature. Consideration of initial and final parts of degradation reactions yields a large amount of information about degradation mechanisms without the need of performing complicated kinetic calculations. Special consideration is given to depolymerization reactions with kinetic chain lengths larger and smaller than polymer chains. The discussion is illustrated by recent investigations by the author and co-workers: The thermal degradation of polytetrafluoroethylene and polymethylmethacrylate in closed systems, and the photodegradation of polymethylmethacrylic acid in aqueous solutions as a function of pH.
Jellinek, H. H.G.
Clarkson College of Technology, Potsdam, N. Y.